DE1495532B2 - PROCESS FOR PRODUCING AN ALKALINE-SOLUBLE MIXED POLYMERISATE - Google Patents
PROCESS FOR PRODUCING AN ALKALINE-SOLUBLE MIXED POLYMERISATEInfo
- Publication number
- DE1495532B2 DE1495532B2 DE19641495532 DE1495532A DE1495532B2 DE 1495532 B2 DE1495532 B2 DE 1495532B2 DE 19641495532 DE19641495532 DE 19641495532 DE 1495532 A DE1495532 A DE 1495532A DE 1495532 B2 DE1495532 B2 DE 1495532B2
- Authority
- DE
- Germany
- Prior art keywords
- ester
- acid
- weight
- alkali
- vinyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D161/00—Coating compositions based on condensation polymers of aldehydes or ketones; Coating compositions based on derivatives of such polymers
- C09D161/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F218/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid or of a haloformic acid
- C08F218/02—Esters of monocarboxylic acids
- C08F218/04—Vinyl esters
- C08F218/08—Vinyl acetate
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D131/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an acyloxy radical of a saturated carboxylic acid, of carbonic acid, or of a haloformic acid; Coating compositions based on derivatives of such polymers
- C09D131/02—Homopolymers or copolymers of esters of monocarboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D135/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical, and containing at least another carboxyl radical in the molecule, or of salts, anhydrides, esters, amides, imides or nitriles thereof; Coating compositions based on derivatives of such polymers
- C09D135/02—Homopolymers or copolymers of esters
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L61/00—Compositions of condensation polymers of aldehydes or ketones; Compositions of derivatives of such polymers
- C08L61/20—Condensation polymers of aldehydes or ketones with only compounds containing hydrogen attached to nitrogen
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Paints Or Removers (AREA)
- Cosmetics (AREA)
Description
können für vielfältige Anwendungszwecke verwendet werden, sei es gemischt mit Füllstoffen und Pigmenten oder auch anderweitig, und solche Anwendungsmöglichkeiten umfassen Oberflächenüberzüge, Papierüberzüge oder -imprägnierung und als Finish für bestimmte Textilien. Die Lösung kann als ein Eisatz für Casein oder als ein Verdickungskolloid in der Emulsionspolymerisation verwendet werden.can be used for a variety of purposes, be it mixed with fillers and pigments or otherwise, and such uses include surface coatings, paper coatings or impregnation and as a finish for certain textiles. The solution can be used as an ice cream for casein or as a thickening colloid in emulsion polymerization.
Mischpolymerisate von Vinylacetat mit Acrylsäure, die in Abwesenheit von Diäthyl- und/oder Dibutylester der Fumar- bzw. Maleinsäure und/oder Dipropylester der Maleinsäure hergestellt werden, ergeben Emulsionen, die auf Zusatz von Ammoniak Agglomerate bilden, die nur langsam dispergierbar sind, wobei die daraus gebildeten Filme etwas spröde sind. Die Zugabe eines äußeren Weichmachers, wie z. B. Dibutylphthalat, hat zur Folge, daß die Emulsionen nicht vollständig löslich in wäßrigem Alkali sind. Die Anwendung eines inneren Weichmachers (eines Comonomeren), wie z. B. eines Acrylsäureester, bewirkt selbst Mischpolymerisation, die wegen der sehr großen Unterschiede in der Reaktionsfähigkeit zwischen dem Vinylester und einem Acrylsäureester schwierig ist. Das erfindungsgemäße Verfahren löst diese Probleme.Copolymers of vinyl acetate with acrylic acid, which in the absence of diethyl and / or dibutyl ester the fumaric or maleic acid and / or dipropyl ester of maleic acid are produced, result in emulsions, which, on the addition of ammonia, form agglomerates which are only slowly dispersible, whereby the films formed therefrom are somewhat brittle. The addition of an external plasticizer, such as. B. dibutyl phthalate, has the consequence that the emulsions are not completely soluble in aqueous alkali. The application of a internal plasticizer (of a comonomer), e.g. B. an acrylic acid ester, causes copolymerization by itself, due to the very large differences in reactivity between the vinyl ester and an acrylic acid ester is difficult. The method according to the invention solves these problems.
Die folgenden Beispiele erläutern die Erfindung, ohne sie zu beschränken. Alle Mengenangaben bedeuten Gewichtsteile.The following examples illustrate the invention without restricting it. All quantities mean parts by weight.
Ein Mischpolymerisat wurde aus den folgenden Bestandteilen helgestellt:A mixed polymer was made from the following components:
TeileParts
Vinylacetat 8 130Vinyl acetate 8 130
Dibutylmaleinat 1 500Dibutyl maleate 1,500
Acrylsäure 370Acrylic acid 370
Hochmolekulare Amylopectin-dextrin 270High molecular amylopectin dextrin 270
Nichtionisches Emulgiermittel 300Nonionic Emulsifier 300
Natrium-dodecyl-benzol-sulfonat.... 10Sodium dodecyl benzene sulfonate .... 10
Kaliumpersulfat 30Potassium persulfate 30
Kaliumbicarbonat 15Potassium bicarbonate 15
Wasser 10 700Water 10 700
Die Umsetzung wurde in einem Reaktionsgefäß aus Tostfreiem Stahl, das mit Rührern und einem Kondensator ausgestattet war, durchgeführt. Das Vinylacetat, die Acrylsäure und das Dibutylmaleinat wurden zusammengemischt. Alle wasserlöslichen Substanzen (außer dem Kaliumpersulfat) wurden mit dem Wasser in dem Reaktionsgefäß, das anschließend auf 60° C erhitzt wurde, vermischt, und dann wurde das Kaliumpersulfat und unmittelbar danach 10 Gewichtsprozent der vermischten Monomeren zugesetzt. Das Gemisch wurde dann unter anfänglichem Rückfluß auf 75 bis 77° C erhitzt, und in diesem Stadium wurden die restlichen Monomeren kontinuierlich innerhalb von 5 bis 7 Stunden zugesetzt, und am Schluß wurde das Gemisch 30 Minuten lang auf 90° C erhitzt. Die erhaltene Emulsion enthielt 50 Gewichtsprozent an festem Material, das eine Teilchengröße bis zu 2 Mikron aufwies, und eine Emulsion wurde allmählich durch Zugabe von Ammoniak unter Erhöhung des pH-Wertes über 7 in eine Lösung überführt. Die Emulsion wurde vor der Zugabe des wäßrigen Ammoniaks mit Wasser auf einen Gehalt an Feststoffen von 20 bis 30°/0 verdünnt. Die aus der Lösung gegossenen Filme besaßen gute Flexibilität und waren klar und widerstandsfähig gegen den Angriff von Wasser.The reaction was carried out in a stainless steel reaction vessel equipped with stirrers and a condenser. The vinyl acetate, acrylic acid and dibutyl maleate were mixed together. All of the water-soluble substances (except for the potassium persulfate) were mixed with the water in the reaction vessel, which was then heated to 60 ° C., and then the potassium persulfate was added, followed immediately by 10% by weight of the mixed monomers. The mixture was then heated to 75-77 ° C under initial reflux, at which stage the remaining monomers were added continuously over 5 to 7 hours and finally the mixture was heated to 90 ° C for 30 minutes. The resulting emulsion contained 50% by weight of solid matter having a particle size of up to 2 microns, and an emulsion was gradually made into a solution by adding ammonia to raise the pH above 7. The emulsion was / 0 diluted prior to the addition of the aqueous ammonia with water to a content of solids from 20 to 30 °. The films cast from the solution had good flexibility and were clear and resistant to attack by water.
Die wäßrige Emulsion eines MischpolymerisatesThe aqueous emulsion of a copolymer
wurde entsprechend der im Beispiel 1 beschriebenen Methode aus den folgenden Bestandteilen hergestellt:was prepared according to the method described in Example 1 from the following ingredients:
TeileParts
Vinylacetat 162,6Vinyl acetate 162.6
Dibutylfumarat 30Dibutyl fumarate 30
Acrylsäure 7,4Acrylic acid 7.4
Hochmolekulares Amylopectin-dextrin 5,4High molecular weight amylopectin dextrin 5.4
Nichtionisches Emulgiermittel 6Nonionic emulsifier 6
Natriumdodecyl-benzol-sulfonat 0,2Sodium dodecyl benzene sulfonate 0.2
Kaliumpersulfat 0,6Potassium persulfate 0.6
*5 Kaliumbicarbonat 0,3* 5 potassium bicarbonate 0.3
Wasser 162Water 162
Der Gehalt an Feststoffen der so erhaltenen Emulsion betrug 55 Gewichtsprozent. Die wie im Beispiel 1 hergestellte Lösung in wäßrigem Ammoniak ergab einen flexiblen, klaren Film, der eine gute Widerstandsfähigkeit gegen den Angriff von Wasser aufwies.The solids content of the emulsion thus obtained was 55% by weight. As in example 1 The prepared solution in aqueous ammonia gave a flexible, clear film that had good resistance against attack by water.
Eine wäßrige Emulsion eines Mischpolymerisats wurde entsprechend der im Beispiel 1 beschriebenen Methode aus den folgenden Bestandteilen hergestellt:An aqueous emulsion of a copolymer was made in accordance with that described in Example 1 Method made from the following components:
TeileParts
Wasser 9450Water 9450
Hochmolekulares Amylopectin-dextrin 270High molecular amylopectin dextrin 270
Nichtionisches Emulgiermittel 270Nonionic Emulsifier 270
Natriumdodecyl-benzol-sulfonat .... 9Sodium dodecyl benzene sulfonate .... 9
Kaliumpersulfat ; 45Potassium persulfate; 45
Dibutylmaleinat 1 800Dibutyl maleate 1,800
Acrylsäure 500Acrylic acid 500
Vinylacetat 6 700Vinyl acetate 6,700
Kaliumbicarbonat 43,2Potassium bicarbonate 43.2
Wasser 172,8Water 172.8
Der Gehalt an Feststoffen der Emulsion betrug Gewichtsprozent. Die Emulsion war leicht löslich in wäßrigem Ammoniak und bildete einen klären, flexiblen Film, der eine gute Widerstandsfähigkeit gegen Wasser aufwies.The solids content of the emulsion was weight percent. The emulsion was easily soluble in aqueous ammonia and formed a clear, flexible film that has good resistance to Had water.
Eine wäßrige Emulsion eines MischpolymerisatesAn aqueous emulsion of a copolymer
wurde entsprechend der in Beispiel 1 beschriebenen Methode aus den folgenden Bestandteilen hergestellt:was prepared according to the method described in Example 1 from the following ingredients:
TeileParts
Vinylacetat 75Vinyl acetate 75
Diäthylmaleinat 30Diethyl maleate 30
Acrylsäure 5Acrylic acid 5
Nonyl-phenyl-äthoxylat (20 Mol) ... 2Nonyl phenyl ethoxylate (20 mol) ... 2
Natrium-lauryl-äther-sulfat 1Sodium Lauryl Ether Sulphate 1
Hydroxyäthylcellulose 2Hydroxyethyl cellulose 2
Natriumbicarbonat 0,25Sodium bicarbonate 0.25
Ammoniumpersulfat 0,25Ammonium persulfate 0.25
Wasser 100,7Water 100.7
Ammoniumpersulfat 0,2Ammonium persulfate 0.2
Wasser 5Water 5
Der Gehalt an Feststoffen der Emulsion betrugThe solids content of the emulsion was
6g 49,2 Gewichtsprozent. Die Emulsion war löslich in wäßrigem Ammoniak und bildete einen klaren flexiblen Film, der eine gute Widerstandsfähigkeit gegenüber Wasser aufwies.6g 49.2 percent by weight. The emulsion was soluble in aqueous ammonia and formed a clear flexible film that has good resistance compared to water.
VergleichsversuchComparative experiment
Es soll der technische Fortschritt nachgewiesen werden, der durch Verwendung eines Esters einer ungesättigten Dicarbonsäure als dritte Monomerenkomponente erzielt werden kann.It is to be demonstrated the technical progress made by using an ester of an unsaturated Dicarboxylic acid can be achieved as the third monomer component.
Es wurde nach der im Beispiel 1 beschriebenen Methode unter Verwendung derselben Komponenten gearbeitet, mit der Ausnahme, daß das im Beispiel 1 verwendete Dibutylmaleinat ersetzt wurde durch die gleiche Anzahl Gewichtsteile zusätzlichen Vinylacetats. Es wurde demgemäß folgende Monomerenzusammensetzung verwendet:It was made according to the method described in Example 1 using the same components worked, with the exception that the dibutyl maleate used in Example 1 was replaced by the equal number of parts by weight of additional vinyl acetate. Accordingly, it became the following monomer composition used:
Vinylacetat 9 630Vinyl acetate 9 630
Acrylsäure 370Acrylic acid 370
Der Gehalt an Feststoffen der Emulsion betrug 49,1 Gewichtsprozent. Die Emulsion wurde auf einen Gehalt an Feststoffen von 25% verdünnt und Ammoniak zur Erzeugung eines pH-Wertes von oberhalb 8,5 hinzugefügt. Das Polymere ging in Lösung, jedoch war der aus dieser Lösung gegossene Film hart und spröde und verschieden von dem gemäß Beispiel 1 erhaltenen widerstandsfähigen und flexiblen Film.The solids content of the emulsion was 49.1 percent by weight. The emulsion was on a Solids content of 25% diluted and ammonia to produce a pH value above 8.5 added. The polymer went into solution, but the film cast from this solution was hard and brittle and different from the tough and flexible film obtained in Example 1.
Claims (7)
sättigten Verbindungen bei einem pH-Wert niede- Die deutschen Auslegeschriften 1 050 058, 1 055 239 riger als 7, dadurch gekennzeichnet, und 1129 285 beschreiben ein der deutschen Auslegedaß ein Vinylester einer niedermolekularen, alipha- schrift 1 044 408 ähnliches Verfahren, jedoch ist auch tisch gesättigten Carbonsäure, Acrylsäure und ein hier die erfindungsgemäße Monomerenkombination Diäthyl- und/oder Dibutylester der Fumar- bzw. io weder beschrieben noch nahegelegt.
Maleinsäure und/oder ein Dipropylester der Ma- In sämtlichen obengenannten Auslegeschriften werleinsäure polymerisiert werden. den somit lediglich Emulsionen oder Dispersionen1. Processes for the production of an alkali-soluble or paints and the like and as a thickener mixed polymer from polymerisable un- 5 are suitable in emulsion polymerisation,
The German Auslegeschriften 1 050 058, 1 055 239 riger than 7, characterized, and 1129 285 describe one of the German Ausleged that a vinyl ester of a low molecular weight, aliphatic 1 044 408 similar process, however, is also table saturated carboxylic acid, acrylic acid and a monomer combination according to the invention diethyl and / or dibutyl ester of the fumaric or io neither described nor suggested.
Maleic acid and / or a dipropyl ester of Ma- werleic acid are polymerized in all of the above-mentioned Auslegeschriften. thus only emulsions or dispersions
merisiert werden. Nach dem erfindungsgemäßen Verfahren kann ausThe process according to the invention for the preparation of dicarboxylic acid is generally not less than an alkali-soluble copolymer of polymer than 5 and advantageously 7 percent by weight, based on soluble unsaturated compounds with a 45 to vinyl ester of the saturated carboxylic acid, and a pH value lower than 7 is characterized, preferably not less than 10 percent by weight that a vinyl ester of a low molecular weight, aliphatic The amount of acrylic acid used is usually saturated carboxylic acid, acrylic acid and diethyl from 3 to 20 percent by weight, based on the total and / or dibutyl ester of fumaric or maleic acid amount of esters present , and preferably and / or a dipropyl ester of maleic acid poly- 50 at least 3.5 percent by weight,
be merized. According to the method according to the invention, from
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GB28214/63A GB1088634A (en) | 1963-07-17 | 1963-07-17 | Alkali soluble polymers |
GB1047765A GB1132107A (en) | 1965-03-12 | 1965-03-12 | Coating compositions |
Publications (2)
Publication Number | Publication Date |
---|---|
DE1495532A1 DE1495532A1 (en) | 1969-01-02 |
DE1495532B2 true DE1495532B2 (en) | 1972-04-06 |
Family
ID=26247545
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19641495532 Pending DE1495532B2 (en) | 1963-07-17 | 1964-07-15 | PROCESS FOR PRODUCING AN ALKALINE-SOLUBLE MIXED POLYMERISATE |
DE19661644774 Pending DE1644774A1 (en) | 1963-07-17 | 1966-03-11 | Polymers |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
DE19661644774 Pending DE1644774A1 (en) | 1963-07-17 | 1966-03-11 | Polymers |
Country Status (1)
Country | Link |
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DE (2) | DE1495532B2 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0024301B1 (en) * | 1979-08-16 | 1984-03-14 | Werkzeugmaschinenfabrik Oerlikon-Bührle AG | Process for manufacturing bevel and hypoid gear pairs |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3242486A1 (en) * | 1982-11-18 | 1984-05-24 | Henkel KGaA, 4000 Düsseldorf | FILM-FORMING ADHESIVE DISPERSIONS AND THEIR USE AS WATER-ACTIVATED COATINGS |
-
1964
- 1964-07-15 DE DE19641495532 patent/DE1495532B2/en active Pending
-
1966
- 1966-03-11 DE DE19661644774 patent/DE1644774A1/en active Pending
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0024301B1 (en) * | 1979-08-16 | 1984-03-14 | Werkzeugmaschinenfabrik Oerlikon-Bührle AG | Process for manufacturing bevel and hypoid gear pairs |
Also Published As
Publication number | Publication date |
---|---|
DE1644774A1 (en) | 1971-07-22 |
DE1495532A1 (en) | 1969-01-02 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
SH | Request for examination between 03.10.1968 and 22.04.1971 |